EP3666813B1 - Self-hardening organic synthetic resin mixture used for additive manufacturing, and application therefor - Google Patents
Self-hardening organic synthetic resin mixture used for additive manufacturing, and application therefor Download PDFInfo
- Publication number
- EP3666813B1 EP3666813B1 EP18844216.4A EP18844216A EP3666813B1 EP 3666813 B1 EP3666813 B1 EP 3666813B1 EP 18844216 A EP18844216 A EP 18844216A EP 3666813 B1 EP3666813 B1 EP 3666813B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- self
- synthetic resin
- resin composition
- organic synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 195
- 229920003002 synthetic resin Polymers 0.000 title claims description 93
- 239000000057 synthetic resin Substances 0.000 title claims description 93
- 239000000654 additive Substances 0.000 title claims description 79
- 230000000996 additive effect Effects 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 60
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 262
- 239000002994 raw material Substances 0.000 claims description 139
- -1 phenol modified furan Chemical class 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 78
- 239000007849 furan resin Substances 0.000 claims description 67
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 62
- 150000001299 aldehydes Chemical class 0.000 claims description 60
- 150000002989 phenols Chemical class 0.000 claims description 51
- 239000007822 coupling agent Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 45
- 150000007524 organic acids Chemical class 0.000 claims description 41
- 229920001568 phenolic resin Polymers 0.000 claims description 41
- 239000005011 phenolic resin Substances 0.000 claims description 41
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229920001169 thermoplastic Polymers 0.000 claims description 35
- 239000004416 thermosoftening plastic Substances 0.000 claims description 35
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 32
- 229910000077 silane Inorganic materials 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 30
- 239000010815 organic waste Substances 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000004576 sand Substances 0.000 claims description 24
- 239000003085 diluting agent Substances 0.000 claims description 23
- 239000012760 heat stabilizer Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 23
- 239000012745 toughening agent Substances 0.000 claims description 23
- 239000003849 aromatic solvent Substances 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 19
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000003929 acidic solution Substances 0.000 claims description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 230000001476 alcoholic effect Effects 0.000 claims description 14
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- 229930091371 Fructose Natural products 0.000 claims description 13
- 239000005715 Fructose Substances 0.000 claims description 13
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000006188 syrup Substances 0.000 claims description 13
- 235000020357 syrup Nutrition 0.000 claims description 13
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 12
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 12
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940095076 benzaldehyde Drugs 0.000 claims description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- XTCHLXABLZQNNN-UHFFFAOYSA-N 3-ethyl-5-methylphenol Chemical compound CCC1=CC(C)=CC(O)=C1 XTCHLXABLZQNNN-UHFFFAOYSA-N 0.000 claims description 7
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005956 Metaldehyde Substances 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 229950000688 phenothiazine Drugs 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 5
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 claims description 5
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 5
- 229940043350 citral Drugs 0.000 claims description 5
- 238000004590 computer program Methods 0.000 claims description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 238000012644 addition polymerization Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 description 98
- 238000003756 stirring Methods 0.000 description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 230000018044 dehydration Effects 0.000 description 14
- 238000006297 dehydration reaction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
- 239000004115 Sodium Silicate Substances 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- 238000010146 3D printing Methods 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 11
- 235000019253 formic acid Nutrition 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000005711 Benzoic acid Substances 0.000 description 9
- 235000010233 benzoic acid Nutrition 0.000 description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 9
- 239000004695 Polyether sulfone Substances 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 229920006393 polyether sulfone Polymers 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 7
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 7
- 229930195725 Mannitol Natural products 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 239000000594 mannitol Substances 0.000 description 7
- 235000010355 mannitol Nutrition 0.000 description 7
- 229920001955 polyphenylene ether Polymers 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 239000000811 xylitol Substances 0.000 description 6
- 235000010447 xylitol Nutrition 0.000 description 6
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 6
- 229960002675 xylitol Drugs 0.000 description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 5
- 239000004299 sodium benzoate Substances 0.000 description 5
- 235000010234 sodium benzoate Nutrition 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical compound [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 description 4
- 229940125758 compound 15 Drugs 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 3
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000004330 calcium propionate Substances 0.000 description 3
- 235000010331 calcium propionate Nutrition 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 239000003279 phenylacetic acid Substances 0.000 description 3
- 229960003424 phenylacetic acid Drugs 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 2
- 229940018563 3-aminophenol Drugs 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000013904 zinc acetate Nutrition 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- ZYZCALPXKGUGJI-DDVDASKDSA-M (e,3r,5s)-7-[3-(4-fluorophenyl)-2-phenyl-5-propan-2-ylimidazol-4-yl]-3,5-dihydroxyhept-6-enoate Chemical compound C=1C=C(F)C=CC=1N1C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C(C)C)N=C1C1=CC=CC=C1 ZYZCALPXKGUGJI-DDVDASKDSA-M 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 description 1
- PSLUFJFHTBIXMW-WYEYVKMPSA-N [(3r,4ar,5s,6s,6as,10s,10ar,10bs)-3-ethenyl-10,10b-dihydroxy-3,4a,7,7,10a-pentamethyl-1-oxo-6-(2-pyridin-2-ylethylcarbamoyloxy)-5,6,6a,8,9,10-hexahydro-2h-benzo[f]chromen-5-yl] acetate Chemical compound O([C@@H]1[C@@H]([C@]2(O[C@](C)(CC(=O)[C@]2(O)[C@@]2(C)[C@@H](O)CCC(C)(C)[C@@H]21)C=C)C)OC(=O)C)C(=O)NCCC1=CC=CC=N1 PSLUFJFHTBIXMW-WYEYVKMPSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 229940127573 compound 38 Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/36—Furfuryl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/097—Sulfur containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/14—Furfuryl alcohol polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
- C08G16/0256—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing oxygen in the ring
- C08G16/0262—Furfuryl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present application relates to organic polymer synthetic materials, and more particularly to a self-curing organic synthetic resin composition for additive manufacturing and uses thereof.
- Three-dimensional printing (3DP), also known as additive manufacturing was put forward by E. Sachs et al. in 1992.
- 3D Printing process materials are ejected in droplets through a nozzle, similar to the way that the inkjet printer works, and the materials are cured layer-by-layer according to a certain path as designed to form the final product.
- the organic synthetic resin for additive manufacturing includes a self-curing furan resin and a self-curing basic phenolic resin.
- An inorganic resin for additive manufacturing is usually a self-curing sodium silicate binder.
- Chinese Patent Publication No. 105949418 A discloses a self-curing furan resin for 3D Printing in aluminum casting.
- Chinese Patent Publication No. 106543687 A discloses a graphene oxide-modified self-curing furan resin for 3D Printing.
- Chinese Patent Publication No. 104086734 A discloses a furan resin for sand 3D Printing.
- These self-curing furan resins facilitate rapid curing at normal temperature and fulfill basic industrial requirements of additive manufacturing.
- these self-curing furan resins have poor resistance to high temperature, displaying a tensile strength of only 0.15 MPa at 1000°C, which leads to the defects such as sand burning and veining during casting. These defects occur more frequently on large-scale cast-iron and steel castings that require high casting temperature, thus limiting the further use of self-curing furan resin binders in large-scale cast-iron and steel castings.
- the self-curing sodium silicate binder is eco-friendly and low-cost compared to the organic resin.
- the self-curing sodium silicate binder has the disadvantages of low tensile strength at normal temperature (about 1.2 MPa), poor collapsibility and difficult sand cleaning process.
- Chinese Patent Publication No. 104923717 A discloses an inorganic binder for sand 3D Printing in non-ferrous metal casting.
- the inorganic binder disclosed herein has a compressive strength of about 4.5 MPa, and a low tensile strength at normal temperature (about 1.2 MPa) due to small-molecule structure and low toughness of the inorganic binder.
- the inorganic binder disclosed herein has a high residual strength at 800°C (about 0.5 MPa) and poor collapsibility, resulting in a difficult sand cleaning process.
- the sodium silicate binder disclosed herein has a usable life in the range of 5-15 min and weak adhesion activity, resulting in low efficiency in producing castings.
- Phenolic resins have different molecular structure compared to furan resins, so that the self-curing basic phenolic resin shows different performances, such as good resistance to high temperature and low strength at normal temperature (only about 1.2 MPa).
- Chinese Patent Publication No. 104817665 A discloses a basic phenolic resin for 3D Printing, which has a low tensile strength at normal temperature (about 1.2 MPa).
- CN101544808 A discloses a composition for impregnating graphite, comprising 5-7 parts of maleimide, 66-67 parts of resol resin, and 25-27 parts of furan resin.
- the prior art fails to solve the problem that a 3D printed object produced by additive manufacturing has poor resistance to high temperature, low tensile strength at normal temperature and poor collapsibility.
- This invention provides a self-curing organic synthetic resin composition for additive manufacturing and uses thereof to address the problem in the prior art that a 3D printed object produced by additive manufacturing has poor resistance to high temperature, low tensile strength at normal temperature and poor collapsibility.
- a self-curing organic synthetic resin composition for additive manufacturing comprising 30-75% by weight of a linear thermoplastic phenolic resin and 25-70% by weight of a phenol modified furan resin.
- the linear thermoplastic phenolic resin is prepared from raw materials A through addition polymerization reaction, and the raw materials A comprise 15-45% by weight of a phenolic compound, 30-60% by weight of an aldehyde compound, 0.2-0.8% by weight of an organic acid or an organic acid salt as a catalyst, and an auxiliary A; the auxiliary A comprises 1-4% by weight of a polymerization inhibitor, 8-28% by weight of an organic solvent, 0.3-0.9% by weight of a coupling agent, 0.1-0.7% by weight of a toughening agent and 1-5% by weight of a modifier, wherein all of the percents by weight are based on the total weight of the raw materials A.
- the phenolic compound in the raw materials A is selected from the group consisting of phenol, p-aminophenol, p-cresol, m-cresol, m-aminophenol, p-nitrophenol, p-chloro-m-xylenol, p-tert-octyl phenol and a combination thereof.
- the aldehyde compound in the raw materials A is selected from the group consisting of formaldehyde and a liquid aldehyde containing two or more carbon atoms; and the liquid aldehyde is selected from the group consisting of acetaldehyde, butyraldehyde, valeraldehyde, terephthalaldehyde, trioxane, metaldehyde, dimethoxymethane, o-chlorobenzaldehyde and a combination thereof.
- the organic acid in the raw materials A is selected from the group consisting of formic acid, acetic acid, p-toluene sulfonic acid, acrylic acid, benzoic acid, propionic acid and a combination thereof.
- the organic acid salt in the raw materials A is selected from the group consisting of zinc acetate, magnesium acetate, sodium benzoate, calcium propionate, aluminum acrylate and a combination thereof.
- the polymerization inhibitor in the raw materials A is molecular, and is selected from the group consisting of hydroquinone, p-benzoquinone, 4-tert-butylcatechol, phenothiazine and a combination thereof.
- the organic solvent in the raw materials A is a polar organic solvent with low molecular weight, and is selected from the group consisting of methanol, ethylene glycol, ethanol, acetone, isopropanol, methyl butanone and a combination thereof.
- the coupling agent in the raw materials A is silane which is selected from the group consisting of silane KH-560, silane KH-550, silane KH-602 and a combination thereof.
- the toughening agent in the raw materials A is selected from the group consisting of polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polyvinyl alcohol and a combination thereof.
- the modifier in the raw materials A is an aromatic solvent oil, which is selected from the group consisting of an aromatic solvent oil S-100, an aromatic solvent oil S-150, an aromatic solvent oil S-200 and a combination thereof, thereby allowing the linear thermoplastic phenolic resin for higher resistance to high temperature.
- the phenol modified furan resin is prepared from raw materials B through addition polymerization reaction, and the raw materials B comprise 12-28% by weight of a phenolic compound, 20-70% by weight of furfuryl alcohol, 5-15% by weight of an aldehyde compound, 0.4-1.2% by weight of an organic acid as a catalyst, and an auxiliary B;
- the auxiliary B comprises 4-16% by weight of a diluent, 0.3-0.7% by weight of a pH regulator, 0.3-0.7% by weight of an aldehyde trapping agent, 0.3-1.3% by weight of a coupling agent, 0-10% by weight of an organic waste liquid, 0.2- 0.6% by weight of a heat stabilizer and 3-9% by weight of an additive, wherein all of the percents by weight are based on the total weight of the raw materials B.
- the phenolic compound in the raw materials B is phenol, bisphenol A, a monoalkyl- or dialkyl-substituted phenol.
- the monoalkyl- or dialkyl-substituted phenol is selected from the group consisting of p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3-methyl-5-ethylphenol, 2,6-di-tert-butyl-4-ethylphenol and a combination thereof.
- the furfuryl alcohol in the raw materials B comprises 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol; and the furfuryl alcohol in the raw materials B has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less.
- the aldehyde compound in the raw materials B is selected from the group consisting of an aqueous formaldehyde solution having 36.5 wt.% formaldehyde, furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde, phenylacetaldehyde, citral and a combination thereof.
- the organic acid in the raw materials B is selected from the group consisting of formic acid, acetic acid, citric acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, phenylacetic acid, succinic acid and a combination thereof.
- the diluent in the raw materials B is selected from the group consisting of methanol, ethanol, isopropanol, furfuryl alcohol, ethylene glycol, toluene, petroleum ether and a combination thereof.
- the pH regulator in the raw materials B is an aqueous alkali metal hydroxide solution having 48 wt.% alkali metal hydroxide, and the alkali metal hydroxide is one or two of sodium hydroxide and potassium hydroxide.
- the aldehyde trapping agent in the raw materials B is an ammonia solution having 25-28 wt.% ammonia.
- the coupling agent in the raw materials B is an aqueous silane which is selected from the group consisting of silane KH-560, silane KH-550, silane KH-602 and a combination thereof.
- the organic waste liquid in the raw materials B is produced by cleaning a printhead of a 3D inkjet printer during 3D inkjet printing in casting, and the organic waste liquid comprises 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol.
- the heat stabilizer in the raw materials B is selected from the group consisting of phosphite, epoxy soybean oil, epoxy ester, pentaerythritol, xylitol, mannitol and a combination thereof.
- the additive in the raw materials B is introduced to improve environmental performance of the phenol modified furan resin and reduce cost in resin production and use, and the additive is one or two of syrup and fructose.
- the invention further provides use of the self-curing organic synthetic resin composition in additive manufacturing, wherein the self-curing organic synthetic resin composition is used for the additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- the water-soluble or alcohol-soluble acidic solution is an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less during 3D additive manufacturing.
- the water-soluble or alcohol-soluble acidic solution is 20-60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- the water-soluble or alcohol-soluble acidic solution is uniformly mixed with raw sand materials to obtain a mixture; a layer of the mixture is laid onto a printing table; the self-curing organic synthetic resin composition is sprayed onto the layer by a piezoelectric printhead according to a 3D model designed by a computer program, wherein the layer is rapidly cured at normal temperature due to the reaction between the self-curing organic synthetic resin composition and water-soluble or alcohol-soluble acidic solution applied on surfaces of the raw sand materials; a next layer of the mixture is laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing; the processes of laying, spraying and curing are repeated until a top layer is completed; and raw sand materials in unprinted areas are removed to obtain a 3D printed final product.
- this invention has the following beneficial effects.
- the self-curing organic synthetic resin composition provided in the invention has advantages of high strength at normal temperature, excellent resistance to high temperature, high activity and excellent collapsibility, so it is suitable for additive manufacturing, and particularly for 3D printing in mold casting.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 1.
- Table 1 Composition of raw materials A Raw materials Amount (wt.% ) Specific materials Phenolic compound 30 Phenol Aldehyde compound 45 Formaldehyde Organic acid 0.5 Formic acid Polymerization inhibitor 2.5 Hydroquinone Organic solvent 18 Methanol Coupling agent 0.6 Silane KH-560 Toughening agent 0.4 Polyvinyl butyral Modifier 3 Aromatic solvent oil S-100
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 2.
- Table 2 Composition of raw materials B
- Phenolic compound 20 Phenol Furfuryl alcohol 45 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less
- Aldehyde compound 10 Aqueous formaldehyde solution having 36.5 wt.% formaldehyde Organic acid 0.8 Formic acid Diluent 10 Methanol PH regulator 0.5 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.8 Silane KH-560
- Organic waste liquid 6 54% by weight of ethylene glycol, 36% by weight of ethanol,
- the self-curing organic synthetic resin composition prepared by this method has a viscosity of 11.5 mpa.s at 25°C, a surface tension of 34 mN/s at 20°C, an impurity content of 0.04%, a free formaldehyde content of 0.12% and a density of 1.086 g/ml at 20°C. It has a tensile strength of 2.16 MPa at normal temperature for 24h, a tensile strength of 1.32 MPa at 1000°C and a residual tensile strength of 0.12 MPa at 1000°C. It has a usable life of 1.2 min at 25°C.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 3.
- Table 3 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 35 p-chloro-m-xylenol and p-tert-octyl phenol with equivalent amount Aldehyde compound 40 Acetaldehyde Organic acid salt 0.3 Zinc acetate Polymerization inhibitor 3 P-benzoquinone Organic solvent 17 Ethylene glycol Coupling agent 0.4 Silane KH-550 Toughening agent 0.3 Polyether sulfone Modifier 4 Aromatic solvent oil S-200
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 4.
- Table 4 Composition of raw materials B
- Raw materials Amount (wt.%) Specific materials and requirements
- Phenolic compound 15 Bisphenol A Furfuryl alcohol 50 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 10 Furfural Organic acid 0.8 Acetic acid Diluent 8 Ethanol PH regulator 0.5 Aqueous solution having 48 wt.% potassium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.8 Silane KH-550 Organic waste liquid 6 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8%
- the self-curing organic synthetic resin composition prepared by this method has a viscosity of 12.0 mpa.s at 25°C, a surface tension of 33 mN/s at 20°C, an impurity content of 0.036%, a free formaldehyde content of 0.16% and a density of 1.105 g/ml at 20°C. It has a tensile strength of 2.24 MPa at normal temperature for 24h, a tensile strength of 1.26 MPa at 1000°C and a residual tensile strength of 0.15 MPa at 1000°C. It has a usable life of 1.4 min at 25°C.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 5.
- Table 5 Composition of raw materials A Raw materials Amount (wt.%) Specific materials
- Phenolic compound 40 P-cresol mixed with m-cresol in any proportion Aldehyde compound 35 Dimethoxymethane mixed with o-chlorobenzaldehyde in any proportion Organic acid 0.4 P-toluene sulfonic acid
- Polymerization inhibitor 2.5 4-tert-butylcatechol
- Organic solvent 16 Ethylene glycol mixed with ethanol in any proportion Coupling agent 0.5 Silane KH-560 mixed with silane KH-550 in any proportion Toughening agent 0.6
- Polyphenylene ether ketone Modifier 5 Aromatic solvent oil S-150
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 6.
- Table 6 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 14 P-cresol, m-cresol and o-cresol with equivalent amount Furfuryl alcohol 52 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 13 Acetaldehyde, paraformaldehyde powders and benzaldehyde with equivalent amount Organic acid 0.6 Benzoic acid and phthalic acid in a weight ratio of 1:2 Diluent 10 Ethylene glycol, toluene and petroleum ether in a weight ratio of 1: 2: 2 PH regulator 0.4 Aqueous solution having 48 wt.% sodium hydro
- the self-curing organic synthetic resin composition prepared by this method has a viscosity of 10.8 mpa.s at 25°C, a surface tension of 36 mN/s at 20°C, an impurity content of 0.043%, a free formaldehyde content of 0.19% and a density of 1.066 g/ml at 20°C. It has a tensile strength of 2.09 MPa at normal temperature for 24h, a tensile strength of 1.35 MPa at 1000°C and a residual tensile strength of 0.14 MPa at 1000°C. It has a usable life of 1.6 min at 25°C.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 7.
- Table 7 Composition of raw materials A Raw materials Amount (wt.%) Specific materials
- Phenolic compound 30 P-chloro-m-xylenol Aldehyde compound 40
- Metaldehyde Organic acid salt 0.5 Magnesium acetate, sodium benzoate, calcium propionate in any proportion
- Hydroquinone and p-benzoquinone in a weight ratio of 1: 2
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 8.
- Table 8 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements
- Phenolic compound 20 Phenol, bisphenol A, p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3 -methyl- 5 -ethylphenol, 2,6-di-tert-butyl-4-ethylphenol in any proportion
- Furfuryl alcohol 45 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 10 Furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde with an equivalent amount Organic acid 1 Formic acid
- the self-curing organic synthetic resin composition prepared by this method has a viscosity of 12.6 mpa.s at 25°C, a surface tension of 33 mN/s at 20°C, an impurity content of 0.051%, a free formaldehyde content of 0.21% and a density of 1.114 g/ml at 20°C. It has a tensile strength of 2.20 MPa at normal temperature for 24h, a tensile strength of 1.27 MPa at 1000°C and a residual tensile strength of 0.17 MPa at 1000°C. It has a usable life of 1.5 min at 25°C.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 9.
- Table 9 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 38 P-nitrophenol Aldehyde compound 44 Valeraldehyde Organic acid salt 0.2 Aluminum acrylate Polymerization inhibitor 2 Phenothiazine Organic solvent 13 Isopropanol Coupling agent 0.4 Silane KH-602 Toughening agent 0.4 Polyphenylene ether ketone Modifier 2 Aromatic solvent oil S-150
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 10.
- Table 10 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements
- Furfuryl alcohol 50 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less
- Aldehyde compound 8 Citral Organic acid 0.5 Malonic acid and phenylacetic acid in a weight ratio of 1: 3 Diluent 8 methanol, ethanol and ethylene glycol with an equivalent amount PH regulator 0.4
- Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammoni
- the self-curing organic synthetic resin composition prepared by this method has a viscosity of 11.9 mpa.s at 25°C, a surface tension of 32 mN/s at 20°C, an impurity content of 0.024%, a free formaldehyde content of 0.22% and a density of 1.124 g/ml at 20°C. It has a tensile strength of 2.28 MPa at normal temperature for 24h, a tensile strength of 1.35 MPa at 1000°C and a residual tensile strength of 0.11 MPa at 1000°C. It has a usable life of 1.6 min at 25°C.
- the self-curing organic synthetic resin composition was prepared through three stages. In which, a linear thermoplastic phenolic resin prepared in stage (1) and a phenol modified furan resin prepared in stage (2) were mixed in a certain weight ratio in stage (3) to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 11.
- Table 11 Composition of raw materials A Raw materials Amount (wt.%) Specific materials
- Phenolic compound 15 P-aminophenol Aldehyde compound 60
- Valeraldehyde Organic acid 0.8
- Benzoic acid Polymerization inhibitor 4
- 4-tert-butylcatechol Organic solvent 13.6
- Acetone Coupling agent 0.9 Silane KH-560 Toughening agent 0.7
- Polyether sulfone Modifier 5 Aromatic solvent oil S-200
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 12.
- Table 12 Composition of raw materials B
- Phenolic compound 12 M-cresol Furfuryl alcohol 70 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5
- Phenylacetic acid Diluent 4 Isopropanol PH regulator 0.7
- Aldehyde trapping agent 0.7
- Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.3 Silane KH-602
- Organic waste liquid 2 54% by weight of ethylene glyco
- Example 7 Compared to Example 6, Example 7 used different raw materials A (as shown in Table 13) and different raw materials B (as shown in Table 14).
- Example 8 Compared to Example 6, Example 8 used different raw materials A (as shown in Table 15) and different raw materials B (as shown in Table 16).
- Example 9 Compared to Example 6, Example 9 used different raw materials A (as shown in Table 17) and different raw materials B (as shown in Table 18).
- Example 10 Compared to Example 6, Example 10 used different raw materials A (as shown in Table 19) and different raw materials B (as shown in Table 20).
- Example 11 Compared to Example 6, Example 11 used different raw materials A (as shown in Table 21) and different raw materials B (as shown in Table 22).
- Example 12 Compared to Example 6, Example 12 used different raw materials A (as shown in Table 23) and different raw materials B (as shown in Table 24).
- the self-curing organic synthetic resin composition was prepared through three stages.
- the linear thermoplastic phenolic resin prepared in stage (1) and the phenol modified furan resin prepared in stage (2) were mixed in a certain weight ratio in stage (3) to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- the linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 25.
- Table 25 Composition of raw materials A
- Raw materials Amount (wt.%) Specific materials Phenolic compound 15-45 Phenol, p-aminophenol, p-cresol, m-cresol, m-aminophenol, p-nitrophenol, p-chloro-m-xylenol, p-tert-octyl phenol and a combination thereof
- Aldehyde compound 30-60 Formaldehyde, acetaldehyde, butyraldehyde, valeraldehyde, terephthalaldehyde, trioxane, metaldehyde, dimethoxymethane, o-chlorobenzaldehyde and a combination thereof
- the phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 26.
- Table 26 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 12-28 Phenol, bisphenol A, p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3 -methyl-5 -ethylphenol, 2,6-di-tert-butyl-4-ethylphenol and a combination thereof
- Furfuryl alcohol 20-70 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5-15
- Aqueous formaldehyde solution having 36.5 wt.% formaldehyde, furfural, acetaldehy
- the self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- the water-soluble or alcohol-soluble acidic solution was an alcoholic sulfonic acid solution having a total acidity of 32% and a free acid of 5% or less.
- the alcoholic sulfonic acid solution was 20% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- the alcoholic sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture.
- a layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the alcoholic sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
- the self-curing organic synthetic resin composition prepared herein had advantages of high strength at normal temperature, excellent resistance to high temperature, high activity and good collapsibility, so a casting mold could be printed by 3D additive manufacturing for casting purpose, and the casting mold printed herein was suitable for casting various metal workpieces, greatly facilitating casting production.
- the self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- the water-soluble or alcohol-soluble acidic solution was an aqueous sulfonic acid solution having a total acidity of 16% and a free acid of 5% or less.
- the aqueous sulfonic acid solution was 60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- the aqueous sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture.
- a layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the aqueous sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
- the self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- the water-soluble or alcohol-soluble acidic solution was an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less.
- the aqueous or alcoholic sulfonic acid solution was 20-60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- the aqueous or alcoholic sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture.
- a layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the aqueous or alcoholic sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
- The present application relates to organic polymer synthetic materials, and more particularly to a self-curing organic synthetic resin composition for additive manufacturing and uses thereof.
- Three-dimensional printing (3DP), also known as additive manufacturing was put forward by E. Sachs et al. in 1992. In a 3D Printing process, materials are ejected in droplets through a nozzle, similar to the way that the inkjet printer works, and the materials are cured layer-by-layer according to a certain path as designed to form the final product.
- Currently, the organic synthetic resin for additive manufacturing includes a self-curing furan resin and a self-curing basic phenolic resin. An inorganic resin for additive manufacturing is usually a self-curing sodium silicate binder.
-
Chinese Patent Publication No. 105949418 A discloses a self-curing furan resin for 3D Printing in aluminum casting.Chinese Patent Publication No. 106543687 A discloses a graphene oxide-modified self-curing furan resin for 3D Printing.Chinese Patent Publication No. 104086734 A discloses a furan resin for sand 3D Printing. These self-curing furan resins facilitate rapid curing at normal temperature and fulfill basic industrial requirements of additive manufacturing. However, these self-curing furan resins have poor resistance to high temperature, displaying a tensile strength of only 0.15 MPa at 1000°C, which leads to the defects such as sand burning and veining during casting. These defects occur more frequently on large-scale cast-iron and steel castings that require high casting temperature, thus limiting the further use of self-curing furan resin binders in large-scale cast-iron and steel castings. - The self-curing sodium silicate binder is eco-friendly and low-cost compared to the organic resin. However, the self-curing sodium silicate binder has the disadvantages of low tensile strength at normal temperature (about 1.2 MPa), poor collapsibility and difficult sand cleaning process.
Chinese Patent Publication No. 104923717 A discloses an inorganic binder for sand 3D Printing in non-ferrous metal casting. The inorganic binder disclosed herein has a compressive strength of about 4.5 MPa, and a low tensile strength at normal temperature (about 1.2 MPa) due to small-molecule structure and low toughness of the inorganic binder. The inorganic binder disclosed herein has a high residual strength at 800°C (about 0.5 MPa) and poor collapsibility, resulting in a difficult sand cleaning process. The sodium silicate binder disclosed herein has a usable life in the range of 5-15 min and weak adhesion activity, resulting in low efficiency in producing castings. - Phenolic resins have different molecular structure compared to furan resins, so that the self-curing basic phenolic resin shows different performances, such as good resistance to high temperature and low strength at normal temperature (only about 1.2 MPa).
Chinese Patent Publication No. 104817665 A discloses a basic phenolic resin for 3D Printing, which has a low tensile strength at normal temperature (about 1.2 MPa). -
CN101544808 A discloses a composition for impregnating graphite, comprising 5-7 parts of maleimide, 66-67 parts of resol resin, and 25-27 parts of furan resin. - The prior art fails to solve the problem that a 3D printed object produced by additive manufacturing has poor resistance to high temperature, low tensile strength at normal temperature and poor collapsibility.
- This invention provides a self-curing organic synthetic resin composition for additive manufacturing and uses thereof to address the problem in the prior art that a 3D printed object produced by additive manufacturing has poor resistance to high temperature, low tensile strength at normal temperature and poor collapsibility.
- The technical solutions of the invention are described as follows.
- A self-curing organic synthetic resin composition for additive manufacturing, comprising 30-75% by weight of a linear thermoplastic phenolic resin and 25-70% by weight of a phenol modified furan resin.
- The linear thermoplastic phenolic resin is prepared from raw materials A through addition polymerization reaction, and the raw materials A comprise 15-45% by weight of a phenolic compound, 30-60% by weight of an aldehyde compound, 0.2-0.8% by weight of an organic acid or an organic acid salt as a catalyst, and an auxiliary A; the auxiliary A comprises 1-4% by weight of a polymerization inhibitor, 8-28% by weight of an organic solvent, 0.3-0.9% by weight of a coupling agent, 0.1-0.7% by weight of a toughening agent and 1-5% by weight of a modifier, wherein all of the percents by weight are based on the total weight of the raw materials A.
- The phenolic compound in the raw materials A is selected from the group consisting of phenol, p-aminophenol, p-cresol, m-cresol, m-aminophenol, p-nitrophenol, p-chloro-m-xylenol, p-tert-octyl phenol and a combination thereof.
- The aldehyde compound in the raw materials A is selected from the group consisting of formaldehyde and a liquid aldehyde containing two or more carbon atoms; and the liquid aldehyde is selected from the group consisting of acetaldehyde, butyraldehyde, valeraldehyde, terephthalaldehyde, trioxane, metaldehyde, dimethoxymethane, o-chlorobenzaldehyde and a combination thereof.
- The organic acid in the raw materials A is selected from the group consisting of formic acid, acetic acid, p-toluene sulfonic acid, acrylic acid, benzoic acid, propionic acid and a combination thereof.
- The organic acid salt in the raw materials A is selected from the group consisting of zinc acetate, magnesium acetate, sodium benzoate, calcium propionate, aluminum acrylate and a combination thereof.
- The polymerization inhibitor in the raw materials A is molecular, and is selected from the group consisting of hydroquinone, p-benzoquinone, 4-tert-butylcatechol, phenothiazine and a combination thereof.
- The organic solvent in the raw materials A is a polar organic solvent with low molecular weight, and is selected from the group consisting of methanol, ethylene glycol, ethanol, acetone, isopropanol, methyl butanone and a combination thereof.
- The coupling agent in the raw materials A is silane which is selected from the group consisting of silane KH-560, silane KH-550, silane KH-602 and a combination thereof.
- The toughening agent in the raw materials A is selected from the group consisting of polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polyvinyl alcohol and a combination thereof.
- The modifier in the raw materials A is an aromatic solvent oil, which is selected from the group consisting of an aromatic solvent oil S-100, an aromatic solvent oil S-150, an aromatic solvent oil S-200 and a combination thereof, thereby allowing the linear thermoplastic phenolic resin for higher resistance to high temperature.
- The phenol modified furan resin is prepared from raw materials B through addition polymerization reaction, and the raw materials B comprise 12-28% by weight of a phenolic compound, 20-70% by weight of furfuryl alcohol, 5-15% by weight of an aldehyde compound, 0.4-1.2% by weight of an organic acid as a catalyst, and an auxiliary B; the auxiliary B comprises 4-16% by weight of a diluent, 0.3-0.7% by weight of a pH regulator, 0.3-0.7% by weight of an aldehyde trapping agent, 0.3-1.3% by weight of a coupling agent, 0-10% by weight of an organic waste liquid, 0.2- 0.6% by weight of a heat stabilizer and 3-9% by weight of an additive, wherein all of the percents by weight are based on the total weight of the raw materials B.
- The phenolic compound in the raw materials B is phenol, bisphenol A, a monoalkyl- or dialkyl-substituted phenol.
- The monoalkyl- or dialkyl-substituted phenol is selected from the group consisting of p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3-methyl-5-ethylphenol, 2,6-di-tert-butyl-4-ethylphenol and a combination thereof.
- The furfuryl alcohol in the raw materials B comprises 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol; and the furfuryl alcohol in the raw materials B has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less.
- The aldehyde compound in the raw materials B is selected from the group consisting of an aqueous formaldehyde solution having 36.5 wt.% formaldehyde, furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde, phenylacetaldehyde, citral and a combination thereof.
- The organic acid in the raw materials B is selected from the group consisting of formic acid, acetic acid, citric acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, phenylacetic acid, succinic acid and a combination thereof.
- The diluent in the raw materials B is selected from the group consisting of methanol, ethanol, isopropanol, furfuryl alcohol, ethylene glycol, toluene, petroleum ether and a combination thereof.
- The pH regulator in the raw materials B is an aqueous alkali metal hydroxide solution having 48 wt.% alkali metal hydroxide, and the alkali metal hydroxide is one or two of sodium hydroxide and potassium hydroxide.
- The aldehyde trapping agent in the raw materials B is an ammonia solution having 25-28 wt.% ammonia.
- The coupling agent in the raw materials B is an aqueous silane which is selected from the group consisting of silane KH-560, silane KH-550, silane KH-602 and a combination thereof.
- The organic waste liquid in the raw materials B is produced by cleaning a printhead of a 3D inkjet printer during 3D inkjet printing in casting, and the organic waste liquid comprises 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol.
- The heat stabilizer in the raw materials B is selected from the group consisting of phosphite, epoxy soybean oil, epoxy ester, pentaerythritol, xylitol, mannitol and a combination thereof.
- The additive in the raw materials B is introduced to improve environmental performance of the phenol modified furan resin and reduce cost in resin production and use, and the additive is one or two of syrup and fructose.
- The invention further provides use of the self-curing organic synthetic resin composition in additive manufacturing, wherein the self-curing organic synthetic resin composition is used for the additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- The water-soluble or alcohol-soluble acidic solution is an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less during 3D additive manufacturing.
- The water-soluble or alcohol-soluble acidic solution is 20-60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- In some embodiments, the water-soluble or alcohol-soluble acidic solution is uniformly mixed with raw sand materials to obtain a mixture; a layer of the mixture is laid onto a printing table; the self-curing organic synthetic resin composition is sprayed onto the layer by a piezoelectric printhead according to a 3D model designed by a computer program, wherein the layer is rapidly cured at normal temperature due to the reaction between the self-curing organic synthetic resin composition and water-soluble or alcohol-soluble acidic solution applied on surfaces of the raw sand materials; a next layer of the mixture is laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing; the processes of laying, spraying and curing are repeated until a top layer is completed; and raw sand materials in unprinted areas are removed to obtain a 3D printed final product.
- Compared to the prior art, this invention has the following beneficial effects.
- (1) The self-curing organic synthetic resin composition has a viscosity of 10-14 mpa.s at 25°C, which meets the requirement of additive manufacturing.
- (2) The self-curing organic synthetic resin composition has a high tensile strength at normal temperature (above 2.0 MPa), while under the same conditions, the self-curing furan resin has a tensile strength of only 1.4 MPa at normal temperature, and the self-curing sodium silicate binder and the self-curing basic phenolic resin share the tensile strength of only 1.2 MPa at normal temperature.
- (3) The self-curing organic synthetic resin composition has excellent resistance to high temperature, since it has a tensile strength of over 1.2 MPa at 1000°C, while under the same conditions, the self-curing furan resin has a tensile strength of only 0.15 MPa at 1000°C.
- (4) The self-curing organic synthetic resin composition has high activity, since it reacts quickly with an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less. During the reaction, it has a usable life in the range of 0.5-2 min at sand temperature of 25°C. While under the same conditions, the self-curing furan resin and the self-curing sodium silicate binder each react with the aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less. During the reaction, the self-curing furan resin has a usable life in the range of 3-7 min, and the self-curing sodium silicate binder has a usable life in the range of 5-15 min.
- (5) The self-curing organic synthetic resin composition has a residual tensile strength of 0.2 MPa or less at 1000°C. Under the same conditions, the self-curing sodium silicate binder has a residual tensile strength of about 0.5 MPa at 1000°C. The contrast proves that the self-curing organic synthetic resin composition has excellent collapsibility, resulting in an easy sand cleaning process in the late stage of casting production.
- (6) An organic waste liquid which is generated during 3D inkjet printing in casting is reapplied to the resin system, reducing the cost of resin production and use, and reducing the environmental pollution.
- (7) Syrup and fructose, as eco-friendly materials, are introduced into the self-curing organic synthetic resin composition to partially replace furfuryl alcohol in raw materials, facilitating the environmental protection.
- (8) The self-curing organic synthetic resin composition is stable, and after a long-term storage, there is neither crystal formation nor changes in performance and indexes.
- The self-curing organic synthetic resin composition provided in the invention has advantages of high strength at normal temperature, excellent resistance to high temperature, high activity and excellent collapsibility, so it is suitable for additive manufacturing, and particularly for 3D printing in mold casting.
- This invention will be described in detail below with reference to various embodiments, and these embodiments are only for illustration and are not intended to limit the present invention.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 1.
Table 1 Composition of raw materials A Raw materials Amount (wt.% ) Specific materials Phenolic compound 30 Phenol Aldehyde compound 45 Formaldehyde Organic acid 0.5 Formic acid Polymerization inhibitor 2.5 Hydroquinone Organic solvent 18 Methanol Coupling agent 0.6 Silane KH-560 Toughening agent 0.4 Polyvinyl butyral Modifier 3 Aromatic solvent oil S-100 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) 30% by weight of a phenolic compound, 0.5% by weight of an organic acid as a catalyst and 2.5% by weight of a polymerization inhibitor were added to an enamel reactor followed by stirring, and then 45% by weight of an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and 18% by weight of an organic solvent, 0.4% by weight of a toughening agent and 3% by weight of a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and 0.6% by weight of silane as a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 2.
Table 2 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 20 Phenol Furfuryl alcohol 45 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 10 Aqueous formaldehyde solution having 36.5 wt.% formaldehyde Organic acid 0.8 Formic acid Diluent 10 Methanol PH regulator 0.5 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.8 Silane KH-560 Organic waste liquid 6 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.4 Phosphite Additive 6 Syrup - Process of producing the phenol modified furan resin was described as follows.
- (1) 20% by weight of a phenolic compound, 10% by weight of an aldehyde compound and 0.8% by weight of an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, 25% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then 0.5% by weight of a pH regulator was added to the enamel reactor to adjust pH of the mixture to about 5.7-6.0, and 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, 6% by weight of an organic waste liquid, 0.4% by weight of a heat stabilizer and 6% by weight of an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and 10% by weight of a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and 0.5% by weight of an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and 0.8% by weight of water-based silane as a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 35% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 65% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition prepared by this method has a viscosity of 11.5 mpa.s at 25°C, a surface tension of 34 mN/s at 20°C, an impurity content of 0.04%, a free formaldehyde content of 0.12% and a density of 1.086 g/ml at 20°C. It has a tensile strength of 2.16 MPa at normal temperature for 24h, a tensile strength of 1.32 MPa at 1000°C and a residual tensile strength of 0.12 MPa at 1000°C. It has a usable life of 1.2 min at 25°C.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 3.
Table 3 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 35 p-chloro-m-xylenol and p-tert-octyl phenol with equivalent amount Aldehyde compound 40 Acetaldehyde Organic acid salt 0.3 Zinc acetate Polymerization inhibitor 3 P-benzoquinone Organic solvent 17 Ethylene glycol Coupling agent 0.4 Silane KH-550 Toughening agent 0.3 Polyether sulfone Modifier 4 Aromatic solvent oil S-200 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) 35% by weight of a phenolic compound, 0.3% by weight of an organic acid salt as a catalyst and 3% by weight of a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then 40% by weight of an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and 17% by weight of an organic solvent, 0.3% by weight of a toughening agent and 4% by weight of a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and 0.4% by weight of silane as a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 4.
Table 4 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 15 Bisphenol A Furfuryl alcohol 50 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 10 Furfural Organic acid 0.8 Acetic acid Diluent 8 Ethanol PH regulator 0.5 Aqueous solution having 48 wt.% potassium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.8 Silane KH-550 Organic waste liquid 6 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.4 Epoxy soybean oil Additive 8 Fructose - Process of producing the phenol modified furan resin was described as follows.
- (1) 15% by weight of a phenolic compound, 10% by weight of an aldehyde compound and 0.8% by weight of an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, 30% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then 0.5% by weight of a pH regulator was added to the enamel reactor to adjust pH of the mixture to about 5.7-6.0, and 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, 6% by weight of an organic waste liquid, 0.4% by weight of a heat stabilizer and 8% by weight of an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and 10% by weight of a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and 0.5% by weight of an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and 0.8% by weight of water-based silane as a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 30% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 70% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition prepared by this method has a viscosity of 12.0 mpa.s at 25°C, a surface tension of 33 mN/s at 20°C, an impurity content of 0.036%, a free formaldehyde content of 0.16% and a density of 1.105 g/ml at 20°C. It has a tensile strength of 2.24 MPa at normal temperature for 24h, a tensile strength of 1.26 MPa at 1000°C and a residual tensile strength of 0.15 MPa at 1000°C. It has a usable life of 1.4 min at 25°C.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 5.
Table 5 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 40 P-cresol mixed with m-cresol in any proportion Aldehyde compound 35 Dimethoxymethane mixed with o-chlorobenzaldehyde in any proportion Organic acid 0.4 P-toluene sulfonic acid Polymerization inhibitor 2.5 4-tert-butylcatechol Organic solvent 16 Ethylene glycol mixed with ethanol in any proportion Coupling agent 0.5 Silane KH-560 mixed with silane KH-550 in any proportion Toughening agent 0.6 Polyphenylene ether ketone Modifier 5 Aromatic solvent oil S-150 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) 40% by weight of a phenolic compound, 0.4% by weight of an organic acid or an organic acid salt as a catalyst and 2.5% by weight of a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then 35% by weight of an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and 16% by weight of an organic solvent, 0.6% by weight of a toughening agent and 5% by weight of a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and 0.5% by weight of silane as a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 6.
Table 6 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 14 P-cresol, m-cresol and o-cresol with equivalent amount Furfuryl alcohol 52 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 13 Acetaldehyde, paraformaldehyde powders and benzaldehyde with equivalent amount Organic acid 0.6 Benzoic acid and phthalic acid in a weight ratio of 1:2 Diluent 10 Ethylene glycol, toluene and petroleum ether in a weight ratio of 1: 2: 2 PH regulator 0.4 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.4 Ammonia solution having 25 wt.% ammonia Coupling agent 1.1 Silane KH-602 Organic waste liquid 4 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.5 Pentaerythritol, xylitol and mannitol in any proportion Additives 4 Syrup and fructose in a weight ratio of 1: 4 - Process of producing the phenol modified furan resin was described as follows.
- (1) 14% by weight of a phenolic compound, 13% by weight of an aldehyde compound and 0.6% by weight of an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, 30% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then 11% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then 0.4% by weight of a pH regulator was added to the enamel reactor to adjust pH of the mixture to about 5.7-6.0, and 11% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, 4% by weight of an organic waste liquid, 0.5% by weight of a heat stabilizer and 4% by weight of an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and 10% by weight of a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and 0.4% by weight of an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and 1.1% by weight of water-based silane as a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 40% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 60% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition prepared by this method has a viscosity of 10.8 mpa.s at 25°C, a surface tension of 36 mN/s at 20°C, an impurity content of 0.043%, a free formaldehyde content of 0.19% and a density of 1.066 g/ml at 20°C. It has a tensile strength of 2.09 MPa at normal temperature for 24h, a tensile strength of 1.35 MPa at 1000°C and a residual tensile strength of 0.14 MPa at 1000°C. It has a usable life of 1.6 min at 25°C.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 7.
Table 7 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 30 P-chloro-m-xylenol Aldehyde compound 40 Metaldehyde Organic acid salt 0.5 Magnesium acetate, sodium benzoate, calcium propionate in any proportion Polymerization inhibitor 2 Hydroquinone and p-benzoquinone in a weight ratio of 1: 2 Organic solvent 24 Methanol, ethylene glycol, ethanol, acetone, isopropanol, methyl butanone in any proportion Coupling agent 0.8 Any of silane KH-560, silane KH-550 and silane KH-602 Toughening agent 0.7 Polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polyvinyl alcohol in any proportion Modifier 2 Aromatic solvent oil S-100 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) 30% by weight of a phenolic compound, 0.5% by weight of an organic acid or an organic acid salt as a catalyst and 2% by weight of a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then 40% by weight of an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and 24% by weight of an organic solvent, 0.7% by weight of a toughening agent and 2% by weight of a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and 0.8% by weight of silane as a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 8.
Table 8 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 20 Phenol, bisphenol A, p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3 -methyl- 5 -ethylphenol, 2,6-di-tert-butyl-4-ethylphenol in any proportion Furfuryl alcohol 45 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 10 Furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde with an equivalent amount Organic acid 1 Formic acid, acetic acid, citric acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, phenylacetic acid, succinic acid in any proportion Diluent 12 Methanol, ethanol, isopropanol, furfuryl alcohol, ethylene glycol, toluene, petroleum ether in any proportion PH regulator 0.4 Aqueous solution having 48 wt.% sodium hydroxide and potassium hydroxide Aldehyde trapping agent 0.3 Ammonia solution having 28 wt.% ammonia Coupling agent 1.3 Silane KH-560 and silane KH-550 in any proportion Organic waste liquid 5 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.5 Phosphite, epoxy soybean oil, epoxy ester, pentaerythritol, xylitol, mannitol with an equivalent amount Additive 4.5 Fructose - Process of producing the phenol modified furan resin was described as follows.
- (1) 20% by weight of a phenolic compound, 10% by weight of an aldehyde compound and 1% by weight of an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, 25% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then 0.4% by weight of a pH regulator was added to the enamel reactor to adjust pH of the mixture to about 5.7-6.0, and 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, 5% by weight of an organic waste liquid, 0.5% by weight of a heat stabilizer and 4.5% by weight of an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and 12% by weight of a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and 0.3% by weight of an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and 1.3% by weight of water-based silane as a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 32% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 68% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition prepared by this method has a viscosity of 12.6 mpa.s at 25°C, a surface tension of 33 mN/s at 20°C, an impurity content of 0.051%, a free formaldehyde content of 0.21% and a density of 1.114 g/ml at 20°C. It has a tensile strength of 2.20 MPa at normal temperature for 24h, a tensile strength of 1.27 MPa at 1000°C and a residual tensile strength of 0.17 MPa at 1000°C. It has a usable life of 1.5 min at 25°C.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 9.
Table 9 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 38 P-nitrophenol Aldehyde compound 44 Valeraldehyde Organic acid salt 0.2 Aluminum acrylate Polymerization inhibitor 2 Phenothiazine Organic solvent 13 Isopropanol Coupling agent 0.4 Silane KH-602 Toughening agent 0.4 Polyphenylene ether ketone Modifier 2 Aromatic solvent oil S-150 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) 38% by weight of a phenolic compound, 0.2% by weight of an organic acid or an organic acid salt as a catalyst and 2% by weight of a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then 44% by weight of an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and 13% by weight of an organic solvent, 0.4% by weight of a toughening agent and 2% by weight of a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and 0.4% by weight of silane as a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 10.
Table 10 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 25 2,6-di-tert-butyl-4-ethylphenol Furfuryl alcohol 50 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 8 Citral Organic acid 0.5 Malonic acid and phenylacetic acid in a weight ratio of 1: 3 Diluent 8 methanol, ethanol and ethylene glycol with an equivalent amount PH regulator 0.4 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.6 Silane KH-560 Heat stabilizer 0.5 Mannitol Additives 6.5 Syrup - Process of producing the phenol modified furan resin was described as follows.
- (1) 25% by weight of a phenolic compound, 8% by weight of an aldehyde compound and 0.5% by weight of an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, 30% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then 0.4% by weight of a pH regulator was added to the enamel reactor to adjust pH of the mixture to about 5.7-6.0, and 10% by weight of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, 0.5% by weight of a heat stabilizer and 6.5% by weight of an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and 8% by weight of a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and 0.5% by weight of an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and 0.6% by weight of water-based silane as a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 34% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 66% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition prepared by this method has a viscosity of 11.9 mpa.s at 25°C, a surface tension of 32 mN/s at 20°C, an impurity content of 0.024%, a free formaldehyde content of 0.22% and a density of 1.124 g/ml at 20°C. It has a tensile strength of 2.28 MPa at normal temperature for 24h, a tensile strength of 1.35 MPa at 1000°C and a residual tensile strength of 0.11 MPa at 1000°C. It has a usable life of 1.6 min at 25°C.
- The self-curing organic synthetic resin composition was prepared through three stages. In which, a linear thermoplastic phenolic resin prepared in stage (1) and a phenol modified furan resin prepared in stage (2) were mixed in a certain weight ratio in stage (3) to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 11.
Table 11 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 15 P-aminophenol Aldehyde compound 60 Valeraldehyde Organic acid 0.8 Benzoic acid Polymerization inhibitor 4 4-tert-butylcatechol Organic solvent 13.6 Acetone Coupling agent 0.9 Silane KH-560 Toughening agent 0.7 Polyether sulfone Modifier 5 Aromatic solvent oil S-200 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) A phenolic compound, an organic acid or an organic acid salt as a catalyst, and a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and an organic solvent, a toughening agent and a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 12.
Table 12 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 12 M-cresol Furfuryl alcohol 70 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5 Phenylacetaldehyde Organic acid 12 Phenylacetic acid Diluent 4 Isopropanol PH regulator 0.7 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.7 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.3 Silane KH-602 Organic waste liquid 2 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.6 Pentaerythritol Additives 3.5 Syrup and fructose in a weight ratio of 2:1 - Process of producing the phenol modified furan resin was described as follows.
- (1) A phenolic compound, an aldehyde compound and an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, half of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then a quarter of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then a pH regulator was added to the enamel reactor, and a quarter of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, an organic waste liquid, a heat stabilizer and an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 30% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 70% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- Compared to Example 6, Example 7 used different raw materials A (as shown in Table 13) and different raw materials B (as shown in Table 14).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 7 were the the the same as those in Example 6.
Table 13 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 39.4 P-nitrophenol Aldehyde compound 30 Metaldehyde Organic acid or organic acid salt 0.2 Propionic acid Polymerization inhibitor 1 Phenothiazine Organic solvent 28 Methyl butanone Coupling agent 0.3 Silane KH-550 Toughening agent 0.1 Polyphenylene ether ketone Modifier 1 Aromatic solvent oil S-100 Table 14 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 15 3-methyl-5-ethylphenol Furfuryl alcohol 33.5 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 12 Citral Organic acid 1.2 Malonic acid Diluent 16 Isopropanol PH regulator 0.7 Aqueous solution having 48 wt.% potassium hydroxide Aldehyde trapping agent 0.7 Ammonia solution having 25-28 wt.% ammonia Coupling agent 1.3 Silane KH-560 Organic waste liquid 10 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.6 Pentaerythritol Additives 9 Syrup - Compared to Example 6, Example 8 used different raw materials A (as shown in Table 15) and different raw materials B (as shown in Table 16).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 8 were the same as those in Example 6.
Table 15 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 45 Phenol and p-chloro-m-xylenol in any proportion Aldehyde compound 33.9 Dimethoxymethane and o-chlorobenzaldehyde in a weight ratio of 2: 1 Organic acid or organic acid salt 0.3 Formic acid, magnesium acetate and sodium benzoate in any proportion Polymerization inhibitor 3 P-benzoquinone Organic solvent 15 Methyl butanone Coupling agent 0.6 Silane KH-602 Toughening agent 0.2 Polyvinyl alcohol Modifier 2 Aromatic solvent oil S-100 Table 16 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 16.3 Phenol, 3-methyl-4-isopropylphenol and 3-methyl-5-ethylphenol with an equivalent amount Furfuryl alcohol 45 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 15 Aqueous formaldehyde solution having 36.5 wt.% formaldehyde Organic acid 0.6 Phthalic acid Diluent 5 Toluene and petroleum ether in any proportion PH regulator 0.3 Aqueous solution having 48 wt.% sodium hydroxide and potassium hydroxide Aldehyde trapping agent 0.3 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.3 Silane KH-560 Organic waste liquid 9 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.2 Mannitol Additives 8 Syrup and fructose in a weight ratio of 1:3 - Compared to Example 6, Example 9 used different raw materials A (as shown in Table 17) and different raw materials B (as shown in Table 18).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 9 were the same as those in Example 6.
Table 17 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 20 Phenol and p-tert-octyl phenol with an equivalent amount Aldehyde compound 59.9 Formaldehyde, acetaldehyde, butyraldehyde and valeraldehyde with an equivalent amount Organic acid or organic acid salt 0.5 Formic acid, acetic acid, p-toluene sulfonic acid, acrylic acid, benzoic acid and propionic acid with an equivalent amount Polymerization inhibitor 2 Hydroquinone, p-benzoquinone, 4-tert-butylcatechol and phenothiazine with an equivalent amount Organic solvent 13.6 Methanol, ethylene glycol, ethanol, acetone, isopropanol and methyl butanone with an equivalent amount Coupling agent 0.7 Silane KH-560, silane KH-550 and silane KH-602 with an equivalent amount Toughening agent 0.3 Polyvinyl butyral, polyether sulfone, polyphenylene ether ketone and polyvinyl alcohol with an equivalent amount Modifier 3 Aromatic solvent oil S-150 Table 18 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 21 2,6-di-tert-butyl-4-ethylphenol Furfuryl alcohol 50 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5 Furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde and phenylacetaldehyde with an equivalent amount Organic acid 0.5 Formic acid, acetic acid, citric acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, phcnylacctic acid and succinic acid with an equivalent amount Diluent 8 Methanol, ethanol, isopropanol, furfuryl alcohol, ethylene glycol, toluene, petroleum ether PH regulator 0.4 Aqueous solution having 48 wt.% potassium hydroxide Aldehyde trapping agent 0.4 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.4 Silane KH-560 Organic waste liquid 8 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.3 Phosphite, epoxy soybean oil, epoxy ester, pentaerythritol, xylitol and mannitol with an equivalent amount Additives 6 Fructose - Compared to Example 6, Example 10 used different raw materials A (as shown in Table 19) and different raw materials B (as shown in Table 20).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 10 were the same as those in Example 6.
Table 19 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 30 P-cresol Aldehyde compound 43.6 Butyraldehyde Organic acid or organic acid salt 0.6 P-toluene sulfonic acid Polymerization inhibitor 2.5 P-benzoquinone Organic solvent 18 Isopropanol and methyl butanone in a weight ratio of 1:2 Coupling agent 0.8 Silane KH-560 and silane KH-550 in any proportion Toughening agent 0.5 Polyvinyl butyral Modifier 4 Aromatic solvent oil S-150 Table 20 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 20.8 O-cresol Furfuryl alcohol 54.5 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 7 Benzaldehyde Organic acid 0.4 Oxalic acid Diluent 6 Toluene PH regulator 0.3 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.3 Silane KH-550 Organic waste liquid 5 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.2 Pentaerythritol Additives 5 Syrup - Compared to Example 6, Example 11 used different raw materials A (as shown in Table 21) and different raw materials B (as shown in Table 22).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 11 were the same as those in Example 6.
Table 21 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 40 P-nitrophenol Aldehyde compound 41.8 Metaldehyde Organic acid salt 0.7 Sodium benzoate Polymerization inhibitor 1 4-tert-butylcatechol Organic solvent 10 Isopropanol Coupling agent 0.9 Silane KH-602 Toughening agent 0.6 Polyether sulfone Modifier 5 Aromatic solvent oil S-200 Table 22 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 24 P-cresol, m-cresol and o-cresol with an equivalent amount Furfuryl alcohol 60.7 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5 Furfural Organic acid 0.8 Citric acid Diluent 4 Isopropanol PH regulator 0.4 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.5 Ammonia solution having 26 wt.% ammonia Coupling agent 0.3 Silane KH-602 Organic waste liquid 1 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.3 Xylitol Additives 3 Fructose - Compared to Example 6, Example 12 used different raw materials A (as shown in Table 23) and different raw materials B (as shown in Table 24).
- Methods for preparing the raw materials A, the raw materials B and a self-curing organic synthetic resin composition for additive manufacturing in Example 12 were the same as those in Example 6.
Table 23 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 45 P-chloro-m-xylenol and p-tert-octyl phenol in a weight ratio of 1:3 Aldehyde compound 30 Formaldehyde and acetaldehyde with equivalent amount Organic acid or organic acid salt 0.8 Formic acid and aluminum acrylate in a weight ratio of 1:5 Polymerization inhibitor 4 P-benzoquinone, 4-tert-butylcatechol in a weight ratio of 1:2 Organic solvent 15.1 Ethanol and isopropanol in a weight ratio of 1:5 Coupling agent 0.9 Silane KH-560 and Silane KH-602 in a weight ratio of 1:35 Toughening agent 0.7 Polyether sulfone and polyvinyl alcohol in a weight ratio of 1:4 Modifier 3.5 Aromatic solvent oil S-200 Table 24 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 28 Bisphenol A and 3-methyl-5-ethylphenol in a weight ratio of 1:2 Furfuryl alcohol 20 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 14.7 Acetaldehyde and benzaldehyde with equivalent amount Organic acid 1.2 Acetic acid and phenylacetic acid in a weight ratio of 1:4 Diluent 15 Isopropanol and toluene in a weight ratio of 1:3 PH regulator 0.7 Aqueous solution having 48 wt.% sodium hydroxide Aldehyde trapping agent 0.7 Ammonia solution having 25-28 wt.% ammonia Coupling agent 1.1 Silane KH-560 Organic waste liquid 10 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.6 Epoxy soybean oil and pentaerythritol in a weight ratio of 1:6 Additives 8 Syrup and fructose in a weight ratio of 1:4 - In conclusion, the self-curing organic synthetic resin composition was prepared through three stages. In which, the linear thermoplastic phenolic resin prepared in stage (1) and the phenol modified furan resin prepared in stage (2) were mixed in a certain weight ratio in stage (3) to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The linear thermoplastic phenolic resin was prepared from raw materials A, and the composition of the raw materials A was shown in Table 25.
Table 25 Composition of raw materials A Raw materials Amount (wt.%) Specific materials Phenolic compound 15-45 Phenol, p-aminophenol, p-cresol, m-cresol, m-aminophenol, p-nitrophenol, p-chloro-m-xylenol, p-tert-octyl phenol and a combination thereof Aldehyde compound 30-60 Formaldehyde, acetaldehyde, butyraldehyde, valeraldehyde, terephthalaldehyde, trioxane, metaldehyde, dimethoxymethane, o-chlorobenzaldehyde and a combination thereof Organic acid or organic acid salt 0.2-0.8 Formic acid, acetic acid, p-toluene sulfonic acid, acrylic acid, benzoic acid, propionic acid, zinc acetate, magnesium acetate, sodium benzoate, calcium propionate, aluminum acrylate and a combination thereof Polymerization inhibitor 1-4 Hydroquinone, p-benzoquinone, 4-tert-butylcatechol, phenothiazine and a combination thereof Organic solvent 8-28 Methanol, ethylene glycol, ethanol, acetone, isopropanol, methyl butanone and a combination thereof Coupling agent 0.3-0.9 Silane KH-560, silane KH-550, silane KH-602 and a combination thereof Toughening agent 0.1-0.7 Polyvinyl butyral, polyether sulfone, polyphenylene ether ketone, polyvinyl alcohol and a combination thereof Modifier 1-5 Aromatic solvent oil S-200 - Process of producing the linear thermoplastic phenolic resin was described as follows.
- (1) A phenolic compound, an organic acid or an organic acid salt as a catalyst, and a molecular polymerization inhibitor were added to an enamel reactor followed by stirring, and then an aldehyde compound was added to the enamel reactor.
- (2) A steam valve was opened to heat the mixture, and the temperature raised to 85-90°C in 25-30 min and was maintained at 85-90°C for 30-40 min.
- (3) The temperature further raised to 100-105°C in 10-20 min and was maintained at 100-105°C for 120-150 min.
- (4) The mixture was subjected to vacuum dehydration until a desired level of dehydration was reached.
- (5) The temperature was dropped to 70-75°C, and an organic solvent, a toughening agent and a modifier were added to the enamel reactor followed by stirring for 60-90 min.
- (6) The temperature was further dropped to 30-35°C, and a coupling agent was added to the enamel reactor followed by stirring for 40-60 min. The mixture prepared herein was unloaded for use.
- The phenol modified furan resin was prepared from raw materials B, and the composition of the raw materials B was shown in Table 26.
Table 26 Composition of raw materials B Raw materials Amount (wt.%) Specific materials and requirements Phenolic compound 12-28 Phenol, bisphenol A, p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3 -methyl-5 -ethylphenol, 2,6-di-tert-butyl-4-ethylphenol and a combination thereof Furfuryl alcohol 20-70 Furfuryl alcohol that includes 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol, and has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less Aldehyde compound 5-15 Aqueous formaldehyde solution having 36.5 wt.% formaldehyde, furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde, phenylacetaldehyde, citral and a combination thereof Organic acid 0.4-1.2 Formic acid, acetic acid, citric acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, phenylacetic acid, succinic acid and a combination thereof Diluent 4-16 Methanol, ethanol, isopropanol, furfuryl alcohol, ethylene glycol, toluene, petroleum ether PH regulator 0.3-0.7 Aqueous solution having 48 wt.% sodium hydroxide and potassium hydroxide Aldehyde trapping agent 0.3-0.7 Ammonia solution having 25-28 wt.% ammonia Coupling agent 0.3-1.3 Silane KH-560, Silane KH-550 and Silane KH-602 Organic waste liquid 0-10 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol Heat stabilizer 0.2-0.6 Phosphite, epoxy soybean oil, epoxy ester, pentaerythritol, xylitol, mannitol and a combination thereof Additives 3-9 One or two of syrup and fructose - Process of producing the phenol modified furan resin was described as follows.
- (1) A phenolic compound, an aldehyde compound and an organic acid as a catalyst were added to an enamel reactor followed by stirring.
- (2) A steam valve was opened to heat the mixture, and after the temperature raised to 70-75°C, half of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 70-75°C for 55-60 min.
- (3) The temperature raised to 80-85°C in 10-20 minutes, and then a quarter of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 80-85°C for 60-90 min.
- (4) The temperature raised to 95-100°C in 10-20 minutes, and then a pH regulator was added to the enamel reactor, and a quarter of furfuryl alcohol was added to the enamel reactor, and the temperature was maintained at 95-100°C for 120-150 min.
- (5) At 95-100°C, an organic waste liquid, a heat stabilizer and an additive were added to the enamel reactor followed by stirring for 50-60 min.
- (6) The temperature was dropped to 60-65°C, and a diluent was added to the enamel reactor followed by stirring for 30-60 min.
- (7) The temperature was dropped to 40-45°C, and an aldehyde trapping agent was added to the enamel reactor followed by stirring for 30-60 min.
- (8) The temperature was dropped to 30-35°C, and a coupling agent was added to the enamel reactor followed by stirring for 30-60 min. The mixture prepared herein was unloaded for use.
- 30% by weight of the linear thermoplastic phenolic resin prepared in stage (1) and 70% by weight of the phenol modified furan resin prepared in stage (2) were added to an enamel reactor followed by stirring. Then, the temperature raised to 35-40°C and was maintained at 35-40°C for 60-90 min. The mixture prepared herein was unloaded, tested and packaged to obtain the self-curing organic synthetic resin composition for additive manufacturing.
- The self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- In 3D additive manufacturing, the water-soluble or alcohol-soluble acidic solution was an alcoholic sulfonic acid solution having a total acidity of 32% and a free acid of 5% or less. The alcoholic sulfonic acid solution was 20% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- During 3D printing process, the alcoholic sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture. A layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the alcoholic sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
- The self-curing organic synthetic resin composition prepared herein had advantages of high strength at normal temperature, excellent resistance to high temperature, high activity and good collapsibility, so a casting mold could be printed by 3D additive manufacturing for casting purpose, and the casting mold printed herein was suitable for casting various metal workpieces, greatly facilitating casting production.
- The self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- In 3D additive manufacturing, the water-soluble or alcohol-soluble acidic solution was an aqueous sulfonic acid solution having a total acidity of 16% and a free acid of 5% or less. The aqueous sulfonic acid solution was 60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- During 3D printing process, the aqueous sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture. A layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the aqueous sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
- The self-curing organic synthetic resin composition was used for additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- In 3D additive manufacturing, the water-soluble or alcohol-soluble acidic solution was an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less. The aqueous or alcoholic sulfonic acid solution was 20-60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- During 3D printing process, the aqueous or alcoholic sulfonic acid solution was uniformly mixed with raw sand materials to obtain a mixture. A layer of the mixture was laid onto a printing table, and then sprayed with the self-curing organic synthetic resin composition by a piezoelectric printhead according to a 3D model designed by a computer program. Due to the reaction between the self-curing organic synthetic resin composition and the aqueous or alcoholic sulfonic acid solution applied on surfaces of the raw sand materials, the layer was rapidly cured at normal temperature. Then a next layer of the mixture was laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing. The processes of laying, spraying and curing were repeated until a top layer was completed. Raw sand materials in unprinted areas were removed to obtain a 3D printed final product.
- Some information is concluded from the above-mentioned embodiments.
- (1) The self-curing organic synthetic resin composition has a viscosity of 10-14 mpa.s at 25°C, which meets the requirement of additive manufacturing.
- (2) The self-curing organic synthetic resin composition has a high tensile strength at normal temperature (above 2.0 MPa), while under the same conditions, the self-curing furan resin has a tensile strength of only 1.4 MPa at normal temperature, and the self-curing sodium silicate binder and the self-curing basic phenolic resin share the tensile strength of only 1.2 MPa at normal temperature.
- (3) The self-curing organic synthetic resin composition has excellent resistance to high temperature, since it has a tensile strength of over 1.2 MPa at 1000°C, while under the same conditions, the self-curing furan resin has a tensile strength of only 0.15 MPa at 1000°C.
- (4) The self-curing organic synthetic resin composition has high activity, since it reacts quickly with an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less. During the reaction, it has a usable life in the range of 0.5-2 min at sand temperature of 25°C. While under the same conditions, the self-curing furan resin and the self-curing sodium silicate binder each react with the aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less. During the reaction, the self-curing furan resin has a usable life in the range of 3-7 min, and the self-curing sodium silicate binder has a usable life in the range of 5-15 min.
- (5) The self-curing organic synthetic resin composition has a residual tensile strength of 0.2 MPa or less at 1000°C. Under the same conditions, the self-curing sodium silicate binder has a residual tensile strength of about 0.5 MPa at 1000°C. The contrast proves that the self-curing organic synthetic resin composition has excellent collapsibility, resulting in an easy sand cleaning process in the late stage of casting production.
- (6) An organic waste liquid which is generated during 3D inkjet printing in casting is reapplied to the resin system, reducing the cost of resin production and use, and reducing the environmental pollution.
- (7) Syrup and fructose, as eco-friendly materials, are introduced into the self-curing organic synthetic resin composition to partially replace furfuryl alcohol in raw materials, facilitating the environmental protection.
- (8) The self-curing organic synthetic resin composition is stable, and after a long-term storage, there is neither crystal formation nor changes in performance and indexes.
Claims (15)
- A self-curing organic synthetic resin composition for additive manufacturing, comprising 30-75% by weight of a linear thermoplastic phenolic resin and 25-70% by weight of a phenol modified furan resin.
- The self-curing organic synthetic resin composition according to claim 1, characterized in that the linear thermoplastic phenolic resin is prepared from raw materials A through addition polymerization reaction, and the raw materials A comprise 15-45% by weight of a phenolic compound, 30-60% by weight of an aldehyde compound, 0.2-0.8% by weight of an organic acid or an organic acid salt as a catalyst, and an auxiliary A; the auxiliary A comprises 1-4% by weight of a polymerization inhibitor, 8-28% by weight of an organic solvent, 0.3-0.9% by weight of a coupling agent, 0.1-0.7% by weight of a toughening agent and 1-5% by weight of a modifier, wherein all of the percents by weight are based on the total weight of the raw materials A.
- The self-curing organic synthetic resin composition according to claim 2, characterized in that the aldehyde compound is selected from the group consisting of formaldehyde and a liquid aldehyde containing two or more carbon atoms; and the liquid aldehyde is selected from the group consisting of acetaldehyde, butyraldehyde, valeraldehyde, terephthalaldehyde, trioxane, metaldehyde, dimethoxymethane, o-chlorobenzaldehyde and a combination thereof.
- The self-curing organic synthetic resin composition according to claim 2, characterized in that the polymerization inhibitor is molecular, and is selected from the group consisting of hydroquinone, p-benzoquinone, 4-tert-butylcatechol, phenothiazine and a combination thereof.
- The self-curing organic synthetic resin composition according to claim 2, characterized in that the coupling agent is silane which is selected from the group consisting of silane KH-560, silane KH-550, silane KH-602 and a combination thereof.
- The self-curing organic synthetic resin composition according to claim 2, characterized in that the modifier is an aromatic solvent oil, which is selected from the group consisting of an aromatic solvent oil S-100, an aromatic solvent oil S-150, an aromatic solvent oil S-200 and a combination thereof.
- The self-curing organic synthetic resin composition according to claim 1, characterized in that the phenol modified furan resin is prepared from raw materials B through addition polymerization reaction, and the raw materials B comprise 12-28% by weight of a phenolic compound, 20-70% by weight of furfuryl alcohol, 5-15% by weight of an aldehyde compound, 0.4-1.2% by weight of an organic acid as a catalyst, and an auxiliary B; and the auxiliary B comprises 4-16% by weight of a diluent, 0.3-0.7% by weight of a pH regulator, 0.3-0.7% by weight of an aldehyde trapping agent, 0.3-1.3% by weight of a coupling agent, 0-10% by weight of an organic waste liquid, 0.2- 0.6% by weight of a heat stabilizer and 3-9% by weight of an additive, wherein all of the percents by weight are based on the total weight of the raw materials B.
- The self-curing organic synthetic resin composition according to claim 7, characterized in that the phenolic compound is phenol, bisphenol A, a monoalkyl- or dialkyl-substituted phenol; the monoalkyl- or dialkyl-substituted phenol is selected from the group consisting of p-cresol, m-cresol, o-cresol, 3-methyl-4-isopropylphenol, 3-methyl-5-ethylphenol, 2,6-di-tert-butyl-4-ethylphenol and a combination thereof.
- The self-curing organic synthetic resin composition according to claim 7, characterized in that the furfuryl alcohol comprises 0.7% or less by weight of residual aldehyde, 0.3% or less by weight of water and 98% or more by weight of furfuryl alcohol; and the furfuryl alcohol has a cloud point of 10°C or less and an acidity of 0.01 mol/L or less.
- The self-curing organic synthetic resin composition according to claim 7, characterized in that the aldehyde compound is selected from the group consisting of an aqueous formaldehyde solution having 36.5 wt.% formaldehyde, furfural, acetaldehyde, paraformaldehyde powders, benzaldehyde, phenylacetaldehyde, citral and a combination thereof; the pH regulator is an aqueous alkali metal hydroxide solution having 48 wt.% alkali metal hydroxide, and the alkali metal hydroxide is one or two of sodium hydroxide and potassium hydroxide; the aldehyde trapping agent is an ammonia solution having 25-28 wt.% ammonia.
- The self-curing organic synthetic resin composition according to claim 7, characterized in that the organic waste liquid is produced by cleaning a printhead of a 3D inkjet printer during 3D inkjet printing in casting, and the organic waste liquid comprises 54% by weight of ethylene glycol, 36% by weight of ethanol, 2% by weight of furan resin and 8% by weight of furfuryl alcohol.
- The self-curing organic synthetic resin composition according to claim 7, characterized in that the additive is introduced to improve environmental performance of the phenol modified furan resin and reduce cost in resin production and use, and the additive is one or two of syrup and fructose.
- Use of the self-curing organic synthetic resin composition of any one of claims 1-12 in additive manufacturing, characterized in that the self-curing organic synthetic resin composition is used for the additive manufacturing in the presence of a water-soluble or alcohol-soluble acidic solution.
- The use of the self-curing organic synthetic resin composition according to claim 13, characterized in that the water-soluble or alcohol-soluble acidic solution is an aqueous or alcoholic sulfonic acid solution having a total acidity of 16-32% and a free acid of 5% or less; the water-soluble or alcohol-soluble acidic solution is 20-60% by weight of the self-curing organic synthetic resin composition for additive manufacturing.
- The use of the self-curing organic synthetic resin composition according to claim 13, characterized in that the water-soluble or alcohol-soluble acidic solution is uniformly mixed with raw sand materials to obtain a mixture; a layer of the mixture is laid onto a printing table; the self-curing organic synthetic resin composition is sprayed onto the layer by a piezoelectric printhead according to a 3D model designed by a computer program, wherein the layer is rapidly cured at normal temperature due to the reaction between the self-curing organic synthetic resin composition and water-soluble or alcohol-soluble acidic solution applied on surfaces of the raw sand materials; a next layer of the mixture is laid down over previous layers followed by spraying the self-curing organic synthetic resin composition and curing; the processes of laying, spraying and curing are repeated until a top layer is completed; and raw sand materials in unprinted areas are removed to obtain a 3D printed final product.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710685162.7A CN109385038A (en) | 2017-08-11 | 2017-08-11 | Self-hardening organic synthetic resin mixture and application thereof for increasing material manufacturing |
PCT/CN2018/099710 WO2019029641A1 (en) | 2017-08-11 | 2018-08-09 | Self-hardening organic synthetic resin mixture used for additive manufacturing, and application therefor |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3666813A1 EP3666813A1 (en) | 2020-06-17 |
EP3666813A4 EP3666813A4 (en) | 2021-08-04 |
EP3666813B1 true EP3666813B1 (en) | 2022-09-14 |
Family
ID=65270886
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18844216.4A Active EP3666813B1 (en) | 2017-08-11 | 2018-08-09 | Self-hardening organic synthetic resin mixture used for additive manufacturing, and application therefor |
Country Status (8)
Country | Link |
---|---|
US (1) | US11434318B2 (en) |
EP (1) | EP3666813B1 (en) |
JP (1) | JP6894578B2 (en) |
KR (1) | KR102283710B1 (en) |
CN (1) | CN109385038A (en) |
ES (1) | ES2927720T3 (en) |
RU (1) | RU2738371C1 (en) |
WO (1) | WO2019029641A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021147581A (en) * | 2020-03-23 | 2021-09-27 | 株式会社リコー | Active energy ray-curable composition for inkjet, and method and apparatus for manufacturing three-dimensionally molded object |
CN112409556A (en) * | 2020-11-27 | 2021-02-26 | 苏州兴业材料科技股份有限公司 | Method for preparing furan resin for casting from waste water |
TWI774165B (en) * | 2020-12-24 | 2022-08-11 | 金隆化學工業股份有限公司 | A method for binder and additive manufacturing. |
CN113248959B (en) * | 2021-05-18 | 2022-07-12 | 深圳优易材料科技有限公司 | High-temperature-wear-resistant anticorrosive paint and preparation method and application thereof |
CN117245101B (en) * | 2023-11-20 | 2024-03-01 | 西安赛隆增材技术股份有限公司 | Additive manufacturing method for electron beam powder bed melting |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4197385A (en) * | 1975-10-16 | 1980-04-08 | Cpc International Inc. | Furan-phenolic resins for collapsible foundry molds |
US4051301A (en) * | 1975-10-16 | 1977-09-27 | Cpc International Inc. | Furan-phenolic resin coated sand for collapsible foundry molds |
US4476191A (en) * | 1981-11-16 | 1984-10-09 | Ppg Industries, Inc. | Resorcinol-aldehyde resin composition for an adhesive system to be applied to glass fibers |
US4478269A (en) * | 1982-02-16 | 1984-10-23 | Qo Chemicals, Inc. | Furan Resin coated aggregate |
JPS6072635A (en) * | 1983-09-28 | 1985-04-24 | Hitachi Chem Co Ltd | Production of casting mold |
JPS6259664A (en) * | 1985-09-10 | 1987-03-16 | Asahi Organic Chem Ind Co Ltd | Resin composition for organic self-curing mold |
JPH0425556A (en) * | 1990-05-21 | 1992-01-29 | Daiwa Taika Renga Senzoushiyo:Kk | Composite material |
JPH05255572A (en) * | 1992-03-13 | 1993-10-05 | Shimizu Corp | Composite material |
DE4243797C2 (en) * | 1992-12-23 | 1997-01-30 | Hoechst Ag | Curable phenolic resin-modified furan resins as binders for putties and coating compositions with improved thermal stability, processes for their production and their use |
JP2003001368A (en) * | 2001-06-20 | 2003-01-07 | Nakakin:Kk | Method for lamination-shaping and lamination-shaped article |
US7807077B2 (en) * | 2003-06-16 | 2010-10-05 | Voxeljet Technology Gmbh | Methods and systems for the manufacture of layered three-dimensional forms |
CN101544808B (en) * | 2009-04-24 | 2010-10-27 | 无锡中强电碳有限公司 | Carbon graphite material soaking special resin and preparation method thereof |
CN101927319A (en) * | 2010-04-29 | 2010-12-29 | 苏州市兴业铸造材料有限公司 | Adhesive applicable for manufacturing casting mold and use thereof |
CN101941044B (en) * | 2010-09-03 | 2012-09-05 | 吴江市液铸液压件铸造有限公司 | Alkaline phenolic resin self-hardening sand |
AU2013359173A1 (en) * | 2012-12-14 | 2015-05-21 | Western Michigan University Research Foundation | Patternless sand mold and core formation for rapid casting |
RU2535704C1 (en) * | 2013-04-18 | 2014-12-20 | Общество С Ограниченной Ответственностью "Группа "Магнезит" | Method of 3d printing on refractory articles |
JP2015193035A (en) * | 2014-03-19 | 2015-11-05 | 群栄化学工業株式会社 | Method of manufacturing three-dimensional laminated formed object |
CN104086734B (en) | 2014-06-26 | 2016-03-30 | 宁夏共享装备有限公司 | A kind of 3D sand mold prints the production method of furan resin for casting |
CN104817665B (en) | 2015-03-04 | 2017-07-07 | 宁夏共享化工有限公司 | A kind of 3D printing alkalescent phenol resin and preparation method thereof |
CN104923717B (en) | 2015-06-04 | 2017-03-29 | 宁夏共享化工有限公司 | A kind of non-ferrous metal 3D sand molds printing inorganic binder and preparation method thereof |
CN105085852A (en) * | 2015-08-04 | 2015-11-25 | 宁夏共享化工有限公司 | Preparation method of low-nitrogen hot core box furan resin for casting |
CN104999031A (en) * | 2015-08-12 | 2015-10-28 | 宁波高新区多维时空科技有限公司 | Rapid manufacturing method for sprayed and cured molding sand |
CN105131516B (en) * | 2015-09-17 | 2018-01-02 | 中南大学 | A kind of preparation for the dusty material that carbon/carbon compound material is prepared for 3D printing |
CN105669208A (en) * | 2016-03-07 | 2016-06-15 | 武汉理工大学 | Phenolic resin coated ceramic powder for laser 3D printing and preparation method thereof |
CN105750478B (en) * | 2016-03-31 | 2017-09-22 | 宁夏共享化工有限公司 | A kind of 3D sand molds printing high-strength high temperature-resistant phenolic resin and preparation method thereof |
CN105949418A (en) * | 2016-07-06 | 2016-09-21 | 宁夏共享化工有限公司 | 3D (three-dimensional) printing resin for aluminum castings and production method thereof |
CN106001394B (en) * | 2016-07-06 | 2018-01-16 | 宁夏共享化工有限公司 | A kind of hard phenolic resin hardening accelerator of 3D molding sand printing heat and preparation method thereof |
CN106543687A (en) * | 2016-11-01 | 2017-03-29 | 宁夏共享化工有限公司 | A kind of modified 3D printing resin of graphene oxide and its production method |
-
2017
- 2017-08-11 CN CN201710685162.7A patent/CN109385038A/en active Pending
-
2018
- 2018-08-09 ES ES18844216T patent/ES2927720T3/en active Active
- 2018-08-09 JP JP2020502412A patent/JP6894578B2/en active Active
- 2018-08-09 WO PCT/CN2018/099710 patent/WO2019029641A1/en unknown
- 2018-08-09 EP EP18844216.4A patent/EP3666813B1/en active Active
- 2018-08-09 KR KR1020207006063A patent/KR102283710B1/en active IP Right Grant
- 2018-08-09 RU RU2020110030A patent/RU2738371C1/en active
-
2020
- 2020-01-14 US US16/742,648 patent/US11434318B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US11434318B2 (en) | 2022-09-06 |
ES2927720T3 (en) | 2022-11-10 |
KR102283710B1 (en) | 2021-07-30 |
WO2019029641A1 (en) | 2019-02-14 |
JP2020530503A (en) | 2020-10-22 |
US20200231732A1 (en) | 2020-07-23 |
JP6894578B2 (en) | 2021-06-30 |
EP3666813A1 (en) | 2020-06-17 |
KR20200037334A (en) | 2020-04-08 |
CN109385038A (en) | 2019-02-26 |
RU2738371C1 (en) | 2020-12-11 |
EP3666813A4 (en) | 2021-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3666813B1 (en) | Self-hardening organic synthetic resin mixture used for additive manufacturing, and application therefor | |
JP6887595B2 (en) | Polyurethane cold box and / or phenolic resin compositions used in the no-bake method and corresponding two-component binder systems, uses, and methods. | |
CN102665960A (en) | Binder composition for the formation of self-curing molds | |
JP2010260101A (en) | Curing agent composition | |
CN103059505A (en) | CO2 cured alkaline phenolic resin and preparation method thereof | |
CN105689636B (en) | Making molds suit | |
JP6062715B2 (en) | Binder composition for mold making | |
JP5250300B2 (en) | Mold manufacturing method | |
JP5430313B2 (en) | Binder composition for mold making | |
CN117320823A (en) | Method for producing binder resin for casting mold | |
JP6770528B2 (en) | Molding kit | |
CN112236247A (en) | Binder composition for mold making | |
CN1017316B (en) | Resin sand for foundry | |
JP6761943B2 (en) | Binder composition for mold molding | |
CN104550651A (en) | Casting resin sand | |
JP2009292952A (en) | Binder for molding material and molded article | |
JP6971412B2 (en) | Blotting agent composition for molding | |
CN104550649A (en) | Nano-scale adhesive for casting mold/core sand | |
JPS5942581B2 (en) | Self-hardening foundry sand composition | |
CN107790616A (en) | Resin casting | |
JPS5819375B2 (en) | Phenolic resin composition for molds | |
JPS6228043A (en) | Binder resin composition for casting | |
JP5944259B2 (en) | Binder composition for mold making | |
JP2747041B2 (en) | Composition for mold | |
JPH0225238A (en) | Production of casting mold |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200309 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20210701 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C08G 65/36 20060101AFI20210625BHEP Ipc: C08G 65/48 20060101ALI20210625BHEP Ipc: C08G 8/10 20060101ALI20210625BHEP Ipc: B33Y 70/00 20200101ALI20210625BHEP Ipc: C09D 161/06 20060101ALI20210625BHEP Ipc: C09D 11/103 20140101ALI20210625BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20220302 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: KOCEL INTELLIGENT MACHINERY LIMITED |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018040765 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1518667 Country of ref document: AT Kind code of ref document: T Effective date: 20221015 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20220914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221214 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221215 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230116 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230114 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602018040765 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
26N | No opposition filed |
Effective date: 20230615 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230711 Year of fee payment: 6 Ref country code: ES Payment date: 20230918 Year of fee payment: 6 Ref country code: AT Payment date: 20230808 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230714 Year of fee payment: 6 Ref country code: DE Payment date: 20230809 Year of fee payment: 6 Ref country code: BE Payment date: 20230818 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230809 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230809 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230831 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230809 |